Art and composition



Un ted States ate This invention relates to novel fluorinated organic compounds and to their preparation.

Hanfo'rd, in U.S. Patent 2,41 1,15 8, discloses that when a compound of the formula X C=CX wherein all the Xs are fluorine, e.g., tetrafiuoroethylene, or one X is hydrogen or halogen, the other three'being fluorine, is reacted with a saturated acid ester, aldehyde or ketone, the product is an w-hydropolyfluorocarbonyl compound. Hanfords reaction is optionally accomplished in the pressence of named catalysts, including alkali metal alkoxides.

It has now been found that diiferent fluorinated compounds can be obtained when from one to two moles of a fluoroolefin of formula CX =CX wherein the Xs are halogen of atomic number 9 to 35, at least two being fluorine, is caused to react with one mole each of an alkali metal alkoxide and either a carbonic or other carboxylic acid ester, followed by acidification of the reaction mixture. Acidification of the reaction mixture yields the desired ,3-alkoxypolyfluorocarbonyl-containing compounds, which can be isolated by conventional techniques. Someof these ,B-alkoxypolyfluorocarbonyl compounds are new. In a slight variation of the procedure,

it has been found that if an amide is substituted for the initial ester, novel aldehydes are produced in the subsequent acidification step.

An object of this invention is, accordingly, provision of a novel synthesis of fi-alkoxypolyfiuorocarboxylic acid esters and p-alkoxypolyfluoroaldehydes and ketones.

Another object is provision of novel fl-alkoxypolyfiuoroaldehydes and ketones of general formula in which X is a halogen of atomic number 9 to 35, A is hydrogen, hydrocarbon, or fluorocarbon, and R is hydrocarbon or fluorocarbon.

Additional objects of the invention are provision of polymers of the novel B-alkoxypolyfluoroaldehydes and of methods for the preparation of the same.

General equations illustrating the monomeric aspects of the invention may be written as follows:

In the production of ketones, 0M

Mon +cxl=cxi+n o00R R 0cX,0X, ;-R

1 Ht 1! R 0 Cxmx, R-- R o CXICXQC R +R OH+M+ Ra In the production of esters, (a (I)M M0R +CX2=OX2+(R O)zC 0- R'1ooXoX2o(oR 2 OM Ht II R ooxloxl 0R )z- R 00XlCXl00R +R,0H+M+ v It has been found that this reaction can proceed further by reacting with a second equivalent of fluorinated olefin to produce ketones,

Patented June 13, 1961 It will be understood that, where R and R differ, a mixture of the two possible products will be obtained.

.In the production of aldehydes,

more than 7 carbon atoms. Among the preferred fluorinated groups are the polyfluorinated and uand w-hydropolyfluorinated alkyl groups;

d. R derived from the acid moiety of the ester employed, may be defined in the same manner as R except that, in general, it will possess no more than {12 carbons. In addition, it may be hydrogen, aromatic or arylaliphatic. It may also be the residue of a dicarboxylic acid, e.g., carbonic or oxalic; Y

e. R is defined in the same manner as R and f. R is an alkyl or halogenated alkyl (including cyclo- 'alkyl) radical of up to 18 carbons.

It-is preferred that, in any given synthesis, all the Rs (except R s) in the compounds employed be identical. Otherwise, a mixture of products will generally be obtained 'as noted.

In accomplishing the reactions of the equations given, the alkoxide and the selected ester or amide are mixed together, generally in an inert organic liquid medium. The fluon'nated olefin is then contacted with the mixture until there is no further pressure change in the system. The reaction mixture is then acidified, and the desired fl-alkoxypolyfluoro ester, ketone, or aldehyde is isolated by distillation or other method known to those skilled in the art.

In one embodiment, a reactor equipped with a gas-tight stirrer, condenser fitted with a manometer and a vacuum tube is charged with source, thermometer, and gas inlet carboxylic acid ester and alkali metal al'koxide. The system is evacuated and flushed with fluoroolefin at a rate such as to maintain a positive pressure on the system, while the temperature is maintained below 0., generally between 15 and 60 C. After reaction is complete, as evidencedby cessation of consumption. of.fluoro-n. olefin, the reaction mixture is acidified, and the salt which separates is removed by filtration. The filtrate is then subjected to distillation to separate the desired ,B-alkoxy- 5 polyfiuoroaldehyde, ester or ketone.

A critical feature of the instant process is the acidification step. The pH required varies somewhat with the starting materials and the nature of the products. In some cases, carbonic acid can be employed. An acid at least of the strength of acetic is sufficient in all cases. For ease in operation, a mineral acid, e-g-, hydrochloric, sulfuric, phosphoric, hydrobromic, etc., or asulfonic acid is generally employed. The amount of acid needed is at least equivalent to the amount of base (alkoxide) initially used.

The process byv which the products of the invention are made is conducted at temperatures which do not exceed 80 C. and are generally in the range of 15 to 60 C. because under these conditions the best balance of product yield and reaction rate is realized.

Pressure is not a critical variable andmay vary from below atmospheric to 400 1b./sq. in. or more. Generally, however, there is no advantage in using pressures above 200,. lb,/ sq. in. andthis value, represents a practical upper pressure limit. The reaction is permitted to proceed until the system has attained essentially static pressure state under the conditions employed.

The alkali metal alkoxides employed are preferably those of sodiumv because of relatively low cost and availability of this metal. Suitable alkoxides are those of alcohols of up to 18 carbons and particularly useful are he lkfitiqsa Qf, hq hqt ain lkano s. ea ffl p seven carbon atoms. Illustrative of such alcqholsarer methanol,v Propanol, uienqll e n ll er rb tyl al ohol. pentanol-2, heptanol-Z, octanol, dodeeanpl, octadecanol, 1H,1H,3H-tetrafiuoropropanol-1, 111,1!1L7H3K1QQQC31111Q2 qh pt aa u rqettn et, IHJH-nmt flmu propanol-l, 1H,1H nonafluoropentanol- 1, 1 H,1 I -l,3I-I -hex-.. afiuorobutanol-l, 4I -l-tetradecafluoroheptanol;4, and the like. Obviously as functional equiyalentsof sodium in the alkoxides employed are the other metals, namely, lithium, potassium" and. cesiurn fAs previously pointed out, these are less preferred than sodiumbecause of their g g cost? The alkali metal alkoxide is used in amount which is at least equimolar of the carboxylic acid "ester. Ifde sired, a larger amount can be used, butolfersno. advantage.

Thefluoroolefin utilized corresponds to CX -CX in which X is a halogen of atomic number 9to 35,21 least. two of the Xs being fluorine. Examples of suitableflfluo roolefins are dichlorodifiuoroethylene, monochlorotriflud roethylene, monobromotrifluoroethylene, dibromodijiuoroethylene, and tetrafiuoroethylene. Inpractice the fluoroolefin is added to provide at least one incletper mole of ester employed. i V

G enerically the reactant, other than the al koxide and, fluoroolefin, may be defined as a carboxylic, compound, corresponding to Z C O ,Y, in which Z, is hydrogen, alkoxy or alkyl, usually of nqtmore than ,l8srcarbons, and' Y is secondary. amino, i.e,, R N- alkpxy, allgoxy..carbonyl or alkoxy carbonylalkyleneof. not morethan 12 carbon atorns The compounds falling withimthepurview of the above general. formula are.of:three types, viz: (a) carbonate, esters, (b) esters ofcarboxylic acids-other than carbonic, andt (c).carboxamides.

As illustrated by the detailed examples, when carbonates are employed the. reaction proceeds to form the alkoxypolyfluoroester and the bis-beta-alkoxypolyfldoro: ketones, as the principal-products. Wheneste rs, other than carbonates or formates are used .theprincipalprpdrf uct is the alkoxypolyfiuoroketone and when, formalfrjlidefij mine are s d i i h a ke ypelx u rq ls 7 In general, any ester of an aliphatic, cycloaliphatie or aromaticmono-n or, dicarboxylic. acid can be used. The

preferred esters are those of alcohols and fluoroalcohols containing not more than 18 carbons and of carboxyhc acids of up to 12 carbon atoms. Examples are methyl propionate, ethyl isobutyrate, methyl laurate, dodecyl acetate, octadecyl formate, diethyl carbonate, dioctyl cario l b y fet ate an ermate. i hyl suec aa dioctyl adip'a te, methyl cyclohexanecarboxylate, butyl benzoate, diamyl phthalate, phenyl acetate, 1 I- I, 1H;hepta fluorobutyl acetate, 11H, lH QH-hexadecafluorononyI butyrate and the like.

In, the preparation of the novel aldehyde. of the invention N,N-dialkylcarboxamid,es are generally useful, al-w thoughalkyl formates can. also beusedg. Specificoperative N,N -dia1kylcarboxamides, include NZN-dimethyIform' amide.N rd ethy nnnam n he i The eac ions. he. nven o o course. takep ce in, the stoichiometric proportions shownby the general equations above, 'Ifhus in the formation of the fl-alkoxyr lvfl brcesters. and; aldeh d he. a o e n, a bo y i l id t .,1 d-e k m t l al sqx de react 1.;1 mo a panama Impuri i s-i 9 es e can ei s c moun ma 11 is esb fi e o c i me r ca v equi e n ts, inwhichevent the ester functions, both as a eac ant-"a d a'' i n ed u kea er he e winner theallgoxidethe fluoroolefin and the amide proceeds, in 131;:1, molar proportions, in the synthesis; of

- it can equal orexceedthe carboxylic acid ester by. 10

or, rnolfejfold, Suitable, media are diethyl ether, te Iay mf t ni .2: i ethQxy 11a n e like- The separation of the various products from the, acidified reactionmixture and, from each other is readily accomplished by methods well known to thoseskilled in the art. Distillation, crystallization, sublimation, vapor phase chromatography, extraction in ion exchange columns, etc., can be utilized, if 'desired,

There follow some examples which illustrate but do not limit the monomeric, aspects of the invention. In these examples, are by- Weight unless Otherwise e ifie systerrrwas evacuatedand tetrafiuoroethylene was bled in'ata rate which maintained a positive pressure of not more than 50 mm., while the temperature was kept below.

25 C. After 4 hours, the rate of addition had decreased from 10 parts in 10 minutes to 10 parts in 40 minutes.

Thethick slurry whichfqrmed; was treated with,20 0 parts of sulfuric acid (1:1 mixture of concentrated and 20% fuming sulfuric acid), filtered, and the solid washed well with diethyl ether. T he'co'mbinedethereal filtrates were concentrated under water vacuum'at room tempera ture togive410parts of crude product. Flash-distillation followed 'by 1a distillation through a-24-inch column packed vvithglassfhelices yielded 282 parts (74% of theory) of methyl fl-metho'xytetrafluoropropionate, B.P. 6671 C; at 49 mm., n 13371-13327, and '70 parts (12% of theory) of 1,5-dimethoxyperfluoro-3-pentanone, B.P. 77 -78.5 C. at 49 mm., n 13177.

A small sample of polyvinyl acetate was dissolved in the methyl p-inethoxytetrafluoropropionate, prepared as above. The-resulting solution was viscous and a film cast therefrom on glass was'clear, tough, and strongly adherent to the glass.

The methyl S-methoxytetrafluoropropionate was further characterized by conversion todimethyl difluoromalon-ate as follows:

A mixture of'9.5 parts of methyl B-methoxytetrafluoropropionate, 1.6 parts of'methanol, and 40 parts of cone. sulfuric acid was placed in a polyethylene bottle and. warmed on a steam bath. After 15 minutes, the resulting solution was stripped of volatile products under vacuum, the distillate poured into water, and then extracted with ether. The ether extract was dried over anhydrous magnesium sulfate, filtered, and concentrated to yield 7.2 parts of crude dimethyl difluoromalonate. After distillation through a spinning-band column, there was obtained 5.14 parts 71%) of dimethyl 'difiuoromalonate; B.P. 70-72, C. at 20 mm., 11 1.3709. The infrared and n-m-r 1 spectra agreed with the structure of dimethyl difluoromalonate.

Analysis-Called. for C H F O C, 35.7; H, 3.6; F, 22.6; N.E., 84. Found: C, 35.4; H, 3.7; F, 22.1; N.E., 84. p

H CH O (CFzh-C-(CFahO OH +OHaOH+Na+ 1,5-dimethoxyoctafluoropentan-3-one A mixture of 10.8 parts of sodium methoxide and 60 parts of dimethyl carbonate (B.P. 90-91 C.) was placed in a 400-ml. reactor fitted with a thermocouple well and inlet tube. After evacuating and flushing with tetrafluoroethylene, agitation was started and tetrafluoroethylene was added at a rate such as to maintain the temperature at 40 C. During the first hour of addition, the pressure was below atmospheric but slowly rose to 40 lb./sq. in. after 2'hours. After 4 hours at 40 lb./sq. in. there was no more uptake of tetrafluoroethylene, and the temperature dropped to that of the room. During this 1 Nuclear magnetic resonance. l

time 41 parts'of tetrafluoroethylene were absorbed of theory). I

The resulting thick slurry was taken up in. ether and treated with 20 parts of 100% sulfuric acid with stirring and cooling. The precipitated sodium bisulfate was removed by filtration and thoroughly washed with ether. The combined ethereal filtrates were treated with 5. parts of sodium fluoride to remove trace amounts of hydrogen fluoride and then concentrated. Distillation through a spinning-band column at 47 mm. yielded, after a forerun of methyl alcohol and dimethyl carbonate, 48 parts of sweet-smelling oil; B.P. 68-80 C. at 47 mm. Careful fractionation through a 30-inch packed column at 11 mm. pressure yielded (1) 6.4 parts (17% of theory) of methyl fi-methoxytetrafluoropropionate, B.P. 4041 C. at 1 1 mm., n 1.3358; (2) 3.2 parts intermediate frac: tion, B.P. 41-48 C.; and (3) 43.9 parts (75% of theory) of 1,5-dimethoxyperfluoropentan-3-one, B.P. 48 C. at 11 mm., 11 1.3168, d 1.477. Total yield of ester and ketone based on sodium methoxide was 92%. Both n-m-r and infrared spectra were in agreement with these structures.

Analysis.-Calcd. for C H F O C, 31.6; H, 3.2; F, 40.0; N.E., 190. N.E., 182.

' Analysis.Calcd. for C7H6F8O3Z C, 29.0; H, 2.1; F,

52.4; N.E., 290. Found: C, 29.1; H, 2.3; F, 52.4;

EXAMPLE HI To a chilled mixture of 74 .parts of methyl acetate and 21.6 parts of sodium methoxide there was added tetrafluoroethylene at a rate which maintained the temperature below 18 C. After 3 hours 44 parts of tetrafluoroethylene had been absorbed. The reaction mixture was poured into ice cold dilute sulfuric acid. The organic layer was dried, and then distilled through a spinningband column to obtain 32 parts (60% of theory) of methyl tetrafluoroethyl ether, BIP. 35-36 C., 11 1.265, d 1.25; 31 parts (22%) of fl-methoxytetrafluoroethyl methyl ketone, B.P. 7981 C., 11 1.3378; and a high boiling residue which contained 43% F. The

infrared and n-m-r spectra of the ketone were in agree-.. ment with the structure of 4-methoxy-3,3,4,4-tetrafluoro-- F., 21.5; N, 15.8. Found: C, 37.8; H, 2.8; F, 21.2; N,

EXAMPLE IV To 21.6 parts of sodium methoxide suspended in 136 parts of methyl benzoate, tetrafluoroethylene was added with shaking at 40 lb./sq. in. while warming to 52 C. The addition of 40.2 parts of tetrafluoroethylene required 5 hours. To the thick slurry which formed, there was added 100 m1. of 6 N sulfuric acid with vigorous shaking. The organic layer was separated and distilled in a short path still under high vacuum. After heating to 250 C. at 0.1 mm. pressure, there remained a considerable amount of undistilled viscous oil which contained 34.05% of F. The distillate was taken up in ether and extracted with sodium bicarbonate. Concentration in vacuo gave 142 parts of an oil which was distilled through a precision fractionation column to give 95.8 parts of methyl benzoate, B.P. 7578.5 C. at 7 mm.; 11 1.5140, and 6.8 parts of p-methoxytetraflu- The infrared and n-m-r spectra of the ketone fraction" agreed with the assigned structure.

Found: C, 31.8; H, 3.3; F, 39.7;

'7 An lys s-- fo 101 813402: C, 50.9,; H, 3.4; F, 32.2. Found: C, 51.2; H, 3.9; F, 31.8.

EXAMPLE V A, mixture of 6.75 parts of sodium methoxide, 14.6 parts of diethyl oxalate, 17.5 parts of tetrahydrofuran, and 29.3 parts of tetrafluoroethylenewas warmed slowly to 50 C. A maximum pressureof 40.0 lb./sq. in. was developed. The reaction appeared to have been completed during the, warmup period as there was no further pressure drop at 50 0., even after 8 hours. The viscous solutionwas poured into cold aqueous 2 N sulfuric acid and extracted with methylene chloride. The organic extracts were dried over magnesium sulfate, concentrated, and flash distilled; The bulk of the product was quite volatile, with a 2-part viscous fraction boiling above 120 C. at 0.01 mm. The more volatile fractions were combined and distilled-through a spinning-band column to give 18.1 parts of oil; B.P. 647l C. at 8-10 mm.; mi 1.3723. The crude material was redistilled twice from phosphorus pentoxide through a spinning-band column. to give a series of fractions; B.P.. 66-71 C. at 8 mm.; n 13611-13635. Infrared and nuclear magnetic resonance spectral analyses showed this to be a mixture of methyl and ethyl estersof u-keto- 'y-alkoxytetrafluorobutanoic acid, where alkoxy is ethoxy and methoxy. A middle fraction (B.P. 67-.68 C., u 1.3622) analyzed for a mixture where the ratio of methyl to ethyl was 1:1.

Analysis.-Calcd. for CqH F404: C, 36.2; H, 3.5; F, 32.8;- N.E., 232. Found: C, 37.6; H, 2.7; F, 29.9 31.1, 30.4; NzE. in ethanol, 232.

The saponification equivalent was 115 or one half the neutral equivalent, further confirming the assigned structure.

The alkyl a-keto- 'y-alkoxytetrafluorobutanoates were furthercharacterized by conversion to a-ketodifluorosuccinic acid as follows:

The above experiment was repeated at 40 C. for 2v hours, The viscous reationmixture was poured into 2N- sulfuric acid and extracted with methylene chloride.

Concentration of the organic extracts gave an oil which was refluxed overnight with sulfuric acid. The

initially insoluble oil had" gone into solution accompanied by considerable etching ofthe glass flask. The strongly acid solution was extracted continuously with etherovernight: Drying andconcentrating the ether extract gave,

a viscous fuming liquid which now. containedonly one peak in the nuclear magnetic, fluorine resonance. spectrum. Taking the syrup up in hot trifiuoroacetic acid, followed by cooling, gave 8.7 parts of white, very hygroscopic crystals; M.P. 113-116 C. Sublimation raised the melting point to 115-116 C. (in a sealed capillary). Infrarednandvnuclear magnetic resonance spectral analyses characterized thissolidas the ot-ketodifluorosuccinic acid. Elementahaualyses were complicated by therextremely hygroscopic character of the acid;

Analysis-:Calcd. For. C H F O C, 28.6; H, 1.2; F, 22:..6.;.N:.E., 84.. Found: C, 26.9; H, 2.0; F, 21.2; N.E., 17.71614 88' (K EXAMPLE VI To. a suspension of 4.8 parts of sodium hydridein 130 of tetrahydrofuran was added 46.4, parts. of 1H,1H, SH-octafluoro-l-pentanol. After the initial vigorous evolution of gas had ceased, the mixture was refluxed for one hour. until all the sodium hydride hadreacted. The resultingmixturewas, filtered to give'a clear solution of the sodium alkoxide. Excess dimet hy l carbonate partslwas added to the solution followed by tetrafluoroethylene- The system was; maintained; below- 401 C; After. 9ursr r r fi qm thylcn bso pt o occurred at lb./sq. in, The orangereaotion mixture wastreated with 2.2 parts of concentrated. sulfuric acid, 114 P r of die hy th tr tion. f. the inorganic.- salts. and concentration gave. a; yellow oil; whichiumedin air; A flash distillation, followed. by aafractionah dis. tillation, indicated two-main boiling-ranges; 8-l-108- at 10 mm. and 94-101" C. at 0.3 mm. The entire. distillate was treated with separate portions, of sodiumzflur oride and; phosphorus. pentoxide. Redistillation .through a precision fractionation column at 8. gave three, main fractionsA, ,B, and C- Fraction C consisted of 15.9 parts of: bis[B'-(-'1'H,1H, 5H octafluoroamyloxy-)tetrafluoroethyl]ketone, B.P.. 128-131, C. at 8 mm.; 11 113189. The infrared spectra. contained a strongcarbonylabsorption at: 5.56 and; proton and fluorine nuclear magnetic resonancespectra agreed withthe. assigned-structure.

A nalysis.--Calcd. for C H F O C, 26.1; H, 0.9; F, 66.1. Found: C, 26.6; H, 1.1; F,.66.6.

The. ketone readily dissolved. in ethanol to format: ethyl hemiketal which could be titrated with aqueous base to give a neutral equivalent, of 684 for. theketone (theory is 690). The pK of; the hemiketal was 9.6. Thisv ketone can be distilled atatmospheric pressure at 278 C. without noticeable decomposition and: is. useful as, a heatrtransfer' fluid.

Fraction, B consisted of. 4.8.parts. of 1-methoxy-5 -(1H, 1H, 5'H-octafiuoroamyloxy)octafluoro 3' pentanone,.

BR. 92-96" C... 33.8 mm.;. n =1.'3=190. The infrared spectra exhibited." a; strong carbonyl absorption at 5.57 1. The proton andfluorine nuclear-magnetic spectra-agreed with the assigned structure.

Analysis.-Calcd. for c H F O C', 26.9; H, 1.2; F, 62.0. .Foundz-C, 27.3; H; 1.3; F, 61.6.

In. a manner similar to Fraction. C ketone, ,the 1 -meth'- oxy 5-(1H,lH,5H-octafluoroamyloxy)octafiuoro 3-pentanone dissolved in ethanol to form a titratable hemiketal. The neutral equivalent of the ketone was thus determined to be 495 as compared to the theroretical value of 490. The pK was likewise 9.6.

Fraction A consisted of 7.5 parts of oil, B.P. 83-90 C. at 8 mm; 11 1.3210. Infrared and nuclear magnetic resonance: spectral analyses indicated this to be a 2:1 mixture of 1-methoxy-5-(1H,1H,5H-octafluoroamyloxy) octafluoro-B-pentanone and a component which contained one less CF CF grouping.

was placed in a. 1-liter, three-neck flask equipped 'witha stirrer, thermometer, and reflux condenser, which-was* connected to an open-end manometer and a. sourcep of The system was evacuated, flushed tetrafluoroethylene was added over a 2-hour period,-with .7 t

the initial 90% being added during the first 40 minutes. The resulting cloudy viscous solution was treated with 65 parts of methanol and then poured into a mixture of 200 parts of concentrated sulfuric acid and 600 parts of ice. After stirring for 20 was extracted with three 150-part portions of diethyl ether. The ethereal solution, which contained the hemiacetal of ,B-methoxytetrafluoropropionaldehyde, was dried over anhydrous calcium sulfate and concentrated to a low volume by distillation through a 30-cm. packedcolumn. The concentrate was then cautiously treated with an excess of phosphorus pentoxide. The volatile material was removed under vacuum, while heatingon a steam bath. Two distillations 01f fresh phosphorus pentoxide gave 53 parts of crude ,B-methoxytetrafluoropropionaldehyde (B.P. 7784 C.), accompanied by extensive fuming and decomposition. phorus pentoxide gave 36 parts (23% of theory) of the aldehyde, B.P. 83-855 C. A center cut was analyzed. Analysis.-Calcd. for C H F O C, 30.0; H, 2.5; F, 47.5. Found: C, 30.8; H, 2.9; F, 47.4.

In another experiment diethyl ether was used as the medium in place of tetrahydrofuran Starting with 54 parts (1.0 mole) of sodium methoxide, 73 parts (1.0 mole) of dimethylformamide, and 70 parts of diethyl ether, 90 parts (90% of theory) of tetrafluoroethylene was added in the same manner as described above at 2528 C. The volatile materials were removed under vacuum into a trap cooled in solid carbon dioxide and en distilled through a low temperature still. In this manner there was obtained 39 parts of methyl trifluorovinyl ether, B.P. -15" C. as identified by infrared spectral analysis. 4 After removal of the methyl trifluorovinyl ether, the reaction mixture was dissolved in 200 parts of water and 500 parts of 6 N hydrochloric acid was added. The aqueous mixture was extracted six times with a total of 280 parts of diethyl ether. The combined ethereal solutions,which contained the hydrate of B-methoxytetrafluoropropionaldehyde, were concentrated and then cautiously added to 150 parts of phosphorus pentoxide with swirl:

ing and stirring. The resulting mixture was refluxed for one-half hour on a steam bath, and the volatile material was removed in vacuo into a trap cooled in solid carbon dioxide. The product was then distilled from phosphorus pentoxide to give 47 parts of ,B-methoxytetrafluoropropionaldehyde, B.P. 83.5-85.5 C. After sitting overnight at roomtemperature, the purest fraction of the aldehyde (B.P. 85.5 C.) had polymerized spontaneously to a white solid melting at 160-180 C. with an initial softening at 130. C. The other fractions also polymerized upon standing. but more slowly.

' The aldehyde function was confirmed by forming a 2,4-dinitrophenylhydrazone and a semicarbazone. The 2,4-dinitrophenylhydrazone was recrystallized from alcoholwater to constant melting point. needles (M.P. 112-112.5 C.)

had an ultraviolet maximum at 3380 A. (log e=4.33).

from; absolute ethanol.

The resulting white platelets were waxy in appearance and melted at '168.5-169 C.,

90% 4 The yellow C. The pure semicarbazone was obtained after eight recrystallizations minutes, thechilled solution Redistillation from fresh ph EXAMPLE VIII A mixture of 27 parts of sodium methoxide, 72 parts of dimethyl carbonate, and 66 parts of tetrahydrofuran was charged into a pressure reactor, which was then mounted on a shaker machine. After flushing the system,

chlorotrifiuoroethylene was introduced slowly, while the I reactor was shaken and the pressure raised to 42 lb./sq. in. at 40 to 43 C. These conditions were maintained for 5 hours. The reaction mixture was acidified with cold dilute sulfuric acid, and the product extracted into ether, dried, tained 4.9% of methyl a-chloro-fi-methoxytrifluoropropionate, B.P. 84 C. at 47 mm., 11 1.3763, and 41.9% l-chloro-2-methoxy-1,2-difluoroethylene, B.P. 57? to 59 C. The ester analyzed:

Analysis-Calcd. for 'C H O ClF C, 29.1; H, 2.9; Cl,

17.2; F, 27.6. Found: C, 29.7; H, 3.2; CI, 17.0; F, 27.6.: A mixture of 6.0 parts of the methyl ot-chloro-B-meth-' oxytrifluoropropionate, prepared as above, 24 parts of concentrated sulfuric acid, 1 part of water, and 1.2 parts of methanol was heated for 20 minutes on a steam bath. Volatile material consisting of 1.1 parts of liquid, r1

1.4081, was removed by distillation. This product was:

mixed with 5 parts of aniline and the resulting solution was allowed to stand overnight at ambient temperature. About 50 parts of water was added directly to the solution and the excess aniline was removed by steam distillation. Filtration of the steam-distilled residue gave 0.8 part of air-dried solid, M.P. 165-172 lized from benzene and then from ture.

a benzene-hexane mixfluoromalonodianilide.

9.1; Cl, 11.6; F, 6.2. Found: C, 58.9; H, 4.0; Cl, 11.3; F, 6.6; N, 9.1.

EXAMPLE IX Example VIII was repeated except that the tetrahydro furan was replaced by 50 parts of ,dimethyl carbonate, the

pressure and temperature were adjusted to 40 lb./sq. in.":

and 35 to 45 6 hours. There was obtained a product which yielded 19.7% of methyl a-chloro-fi-methoxytrifluoropropionate and 61.6% of 1-chloro-2-methoxy-1,Z-difluoroethylene.

EXAMPLE x Tetrafluoroethylene was added at 30 to 40 lb./sq. in. and 40 C. over a 9-hour reaction period to a reaction mixture containing 112 parts of bis(1H,1H,5H-octafluoro)-amyl carbonate, 44 parts of tetrahydrofuran, and 74.5 parts of'an After removal of unreacted-1H,1H,5H-octafluoroamyl alof colorless liquid,

cohol, there was obtained 54.9 parts B.P. 85 to 87 C./0.5 mm., r'z 1.3181. Infrared, refractive index,

., ketone.

C.) and a methyl hemiconcentrated and distilled. There was 013- C., which was crystal-.:

The product melted at 177-178 C. and infrared. analysis was in agreement with the structure of chlor0- C. respectively and the reaction timewas ether solution containing 63.3 parts of sodium 1H,1H,5Hoctafluoroamylate. The mixture was poured over ice and acidified with hydrochloric acid. The

shed with water,

and n-m-r spectra showed the product to be bis[p (1H,1H,5H octaflnoroamyloxy)tetrafluoroethyl] In addition to the disclosure at the examples tit-tailed 11 above. the, following. table shows other reactants and: products-in accordance; with the invention:

Ethers suchasv diethyl ether, alkanes of the C, to: C1 range, cycloalkanes, andthelike are suitable media.

Table Fluoroolefin- Alkoxlde Ester or Amide Product fi. CF:=CF2...-- NaOCnHas CHnCOOCnHzu (311E250 (CFa) C-OH|.

i C FFCFz..." NaO CmHn 0 C (0 CraHrD CraHuO (CFfir-E-O CrsHu.

. 1 ll CFFQFr.--" NBOCaHu 0O(0Cs 17)2 051111 (CF)r--C(CF2)20CsH17- ll ll QF'F-C F1---" N80 CHI) Fz)!C F'5------- CH:C-0 CHKC Fxhc F] C FKC F):CH10(CF:)PC-CH3.

' II C Fa=C.F.:..... NaO CHa(C F2) 3H CH;(CHr)zC O 0 CHMC F9311---" H(CF2)BCHIO (CFa)r-C (0H,)1CH9.

|l- CFFUF2.... NaOCH:-CFr-CHF:.--- H-C-N(C:H|): CF:-CHFCF:CH O(CFz)r-C-H.

The monomeric fl-alkoxypolyfluoroaldehydes; ketones and esters are in general colorless liquids to'solids with melting and boiling points increasing with their molecular weight. The liquids, and the normal solidsat elevated temperature, are good organic solvents and are thereforeuseful as reaction media involving reactants dihicultly solublet in. conventional reaction media. They are also useful. aszsolvents in casting polymeric films' (see Example I). Some also offer utility in conventional stable liquidoutlets, e-.g.-, .as brake fiuidsand the like.

The: novel flealkoxypolyfluoroaldehydes of this invention: are generically polymerizable and hence are precursors of both homopolymers and copolymers, themselves useful in the production of-films, fibers, bristles and the-like. Polymerization is conveniently effected by-introducingmonomeric B-alkoxypolyfluoroaldehyde into anagitated inert: reaction medium containing an =anionic.initiator and maintained at a temperature below- 0- C. Polymer separates and isrecoveredzbyfiltration orother method knownto those skilled inthe art.

Suitable comonomers for copolymerization with the fl-alkoxypolyfluoroaldehydes of this: invention include thiocarbonyl difiuoride, carboxaldehydes, polyfluoroaldehydes, etc.

Polymerization of the compoundsof the invention is illustrated in the following example (note also Example- Samples. of distilled 9-methoxytetrafluoropropionalder hyde ('1.5ml'.), prepared as in Example VH, were purified by gas chromatography ona 12. 19%" column of a silicone oil supported on firebrick and heated to 140 C. Helium. flow rates .were about 500ml. perminute. The samples. were. collected in traps suitable for polymerization. experiments: by cooling; witlrsolidcarbon dioxide. After the. aldehyde had beencollected, 2.0. ml. of sodiumdried ether wasv introduced into the. trap by meansof, a:

hypodermic. syringe. Then ca. 0.05- cc. ofcatalystwas added. Among the catalysts which initiated polymeriza? tion at 80 were a-toluenethiol. sodium salt, triphenyl phosphine, triethyl phosphite,.pyridine, and piperidine. The, polymersformed in the ether solution were insoluble. They were washed with petroleum ether and could bepressed into self-supporting films at 90 C. Thesefilms. are useful as wrapping foils and insimilar.applications.

' The polymerizationofthe p.-alkoxypolyfluoroaldehydes is effected in, a reaction medium which, preferably, is a:

nonsolvent for the polymer but is. asolvent for 111161110110? mer. The medium is also one which remains liquid under. the temperature conditions used in the polymerization.

(5- temperature of about. 15-80. C., a. fluoroolefin-of the.-

The' amount of reaction medium canbefrom 1.5 to 10.00. or more. times the weight of the monomeric B- alkoxypolyfluoroaldehyde depending upon whether the polymerization is being carried out by a batch or continuous method.

Thepolymerization is effected with anionic initiators. Examples of'such are dimethylformamide, trihydrocarbon' phosphines, stibines,. and arsines of'the type disclosed in US. 2,768,994; the onium salts, includingquaternary ammonium salts and quaternary phosphonium salts. disclosed in'theapplication of H; H. Goodman et -al., US. Serial No. 521,878, filed July 13, 1955; and alkyllphosphites, ,etc.

The amount of. catalyst canvary from 0.1% to about. 10% or more by weight of the monomeric fl-alkoxypolyfluoroaldehyde. In general good results are obtained when the catalyst concentration is from 1% to' 5%v by weight of the monomeric fl-alkoxyfiuoroaldehyde.

The polymerization of the fl alkoxypolyfluoroaldehyde is effected at'temperatures. which can be as low as thefreezing point. of the. reaction medium or as high as 3.0.- C. As a rule'the best'results from the standpoint of. polymer'quality and'reaction'rate are realized at temperatures in the range of C. to.-30 C. and the polymerization isusually carried out within this temperature range.

Since obvious modifications in the invention will be evident torthoseskill'edin the chemical arts, I propose to beiboundsolelyby the. appended claims.

The embodiments'of the invention in which an, mm. sive property or privilege'is claimed are defined as follows:

-1. .The' process which comprises sequentially- (1), conta'cting; at a temperature ofabout 1580C., a .fluoro-' olefinof the formula CX =CX' wherein X is halogen of atomic number 9 to 35. at least two Xs heingflilorine', with a liquid reaction'mixture ofan alkali'metalalkoxidecont-aining up to 18 carbon atoms and a member offtlie. group consisting of carboxylicacid esters ofsaturated alcohols and fiuoroalcohols containing up to18carbon" atoms. and carboxylic acids containing up to 12/ carbonatoms and N,N-dialkyl carboxamides (2) acidifying said liquidreaction: mixture, and- (3 )1 separating from the reaction mixture a. member "of .the group consisting of p-alle' oxypolyfiuorocarboxylic acid esters, fi-fllkOXYPOlYfiHOI'O aldehydesand fl-alkoxypolyfluoroketones 2. The: process of.- claiml in: which. the contacttemperature of the fiuoroolefinl and the liquid reactiommixture is.ab011t:15- 60.? C.

3. The process-which..comprises (1) contacting, ata-a formula CX =CX wherein X is halogen of atomic number 9 to 35, at least two Xs being fluorine, with a liquid reaction mixture comprising at least equimolar quantities of an alkali metal al-koxide containing up to 18 carbon atoms and a member of the group consisting of carboxylic acid esters of saturated alcohols and fluoroalcohols containing up to 18 carbon atoms and carboxylic acids containing up to 12 carbon atoms and N,N-dial=kyl carboxamides, (2) acidifying said reaction mixture, and (3) thereby producing at least one member of the group consisting of fi-alkoxypolyfluorocarboxylic acid esters, fi-alkoxypolyfluoroaldehydes and B-alkoxypolyfluoroketones.

4. The process of claim 3 in which the fluoroolefin is contacted with the liquid reaction mixture until absorption thereof substantially ceases.

5. The process of claim 4 in which the contact temperature of the fluoroolefin and the liquid reaction mixture is about 60 C.

6. The process which comprises sequentially (1) contacting an alkali metal methoxide and dimethyl carbonate, in admixture in liquid phase and at a temperature of about 15-80 C., with tetrafluoroethylene, (2) acidifying the resultant reaction mixture, and (3) subsequently separating at least one member of the group consisting of methyl 8-methoxytetrafluoropropionate and 1,5-dimethoxyperfluoro-3-pentanone therefrom.

7. The process which comprises sequentially (1) contacting an alkali metal methoxide and methyl acetate, in admixture in liquid phase and at a temperature of not more than about 80 C., with tetrafiuoroethylene, (2) acidifying the resultant reaction mixture, and (3) subsequently separating fi-methoxytetrafiuoroethyl methyl ketone therefrom.

8. The process which comprises sequentially (1) contacting an alkali metal methoxide and methyl benzoate, in admixture in liquid phase and at a temperature of about 15-80 C., with tetrafluoroethylene, (2) acidifying the resultant reaction mixture and (3) subsequently separating fl-methoxytetrafluoropropiophenone therefrom.

9. The process which comprises sequentially (1) contacting an alkali metal methoxide and diethyl oxalate, in admixture in liquid phase and at a temperature of about 1580 C., with tetrafluoroethylene, (2) acidifying the resultant reaction mixture, and (3) subsequently separating an ester of a-keto-y-alkoxytetrafluorobutanoic acid, alkoxy being a member of the group consisting of methoxy and ethoxy, therefrom.

10. The process which comprises sequentially (1) contacting an alkali metal alkoxide of 1H,1H,5I-I-octafluorol-pentanol and dimethyl carbonate, in admixture in liquid phase and at a temperature of about 1580 C., with tetrafluoroethylene, (2) acidifying the resultant reaction mixture, and (3) subsequently separating at least one '14 member of the group consisting of bis[fl-(1H,1H,5H- octafiuoroamyloxy)tetrafiuoroethylJketone and l-methoxy S (1H,1H,5H-octafluoroamyloxy)octafluoro-3-pentanone therefrom.

11. The process which comprises sequentially (1) contacting an alkali metal methoxide and dimethylforrnamide, in admixture in liquid phase and at a temperature of about 1580 C., with tetrafluoroethylene, (2) acidifying the resultant reaction mixture, and 3) subsequently recovering fl-methoxytetrafiuoropropionaldehyde therefrom.

12. In the preparation of a member of the group consisting of fi-alkoxypolyfluorocarboxylic acid esters, fi-alkoxypolyfluoroaldehydes and fl-alkoxypolyfluoroketones, the sequential steps of (l) contacting an alkali metal alkoxide containing up to 18 carbon atoms and a member of the group consisting of carboxylic acid esters of saturated alcohols and fiuoroalcohols containing up to 18 carbon atoms and carboxylic acids containing up to 12 carbon atoms and N,N-dialkyl carboxamides, in admixture in liquid phase and at a temperature of about l5-80 C., with a fluoroolefin of the formula CX =CX wherein X is halogen of atomic number 9 to 35, at least two Xs being fluorine, and (2) subsequently acidifying the resultant reaction mixture.

13. A compound of the formula ROCF CX COA, wherein R is a member of the group consisting of hydrocarbon and fluorocarbon containing up to 18 carbon atoms, X is halogen of atomic number 9 to 35, and A is a member of the group consisting of hydrogen and saturated hydrocarbon and fluorocarbon containing up to 12 carbon atoms.

14. 1,S-dimethoxyperfluoro-3-pentanone.

15. 4-methoxy-3,3,4,4-tetrafiuoro-2-butanone.

16. fl-Methoxytetrafluoropropiophenone.

17. Bis p (1H,1H,5H octafluoroamyloxy)tetrafluoroethyl]ketone.

18. 1-methoxy-5-(1H,1H,5H octafiuoroamyloxy)octafluoro-S-pentanone.

19. 5-Methoxytetrafiuoropropionaldehyde.

20. A polymer of a compound of claim 13 wherein A is hydrogen.

21. A polymer of B-methoxytetrafluoropropionaldehyde.

22. The polymer of claim 20 in the form of a film.

23. The process which comprises contacting a compound of claim 13 wherein A is hydrogen in an inert liquid medium with an anionic polymerization initiator at a temperature between about minus C. and plus 30 C. and thereby polymerizing said compound.

References Cited in the file of this patent UNITED STATES PATENTS 2,411,158 Hanford Nov. 19, 1946 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 2,988 537' June 13, 1961 Douglas} W, Wiley It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below,-

Column 13,, lines 29 and 3O. for "not more than about 80 C." read about 15-80 C.

Signed and sealed this 19th day of December 1961,

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents USCOMM-DC 

1. THE PROCESS WHICH COMPRISES SEQUENTIALLY (1) CONTACTING, AT A TEMPERATURE OF ABOUT 15-80*C., A FLUOROOLEFIN OF THE FORMULA CX2=CX2, WHEREIN X IS HALOGEN OF ATOMIC NUMBER 9 TO 35, AT LEAST TWO X''S BEING FLUORINE, WITH A LIQUID REACTION MIXTURE OF AN ALKALI METAL ALKOXIDE CONTAINING UP TO 18 CARBON ATOMS AND A MEMBER OF THE GROUP CONSISTING OF CARBOXYLIC ACID ESTERS OF SATURATED ALCOHOLS AND FLUOROALCOHOLS CONTAINING UP TO 18 CARBON ATOMS AND CARBOXYLIC ACIDS CONTAINING UP TO 12 CARBON ATOMS AND N,N-DIALKYL CARBOXAMIDES, (2) ACIDIFYING SAID LIQUID REACTION MIXTURE, AND (3) SEPARATING FROM THE REACTION MIXTURE A MEMBER OF THE GROUP CONSISTING OF B-ALKOXYPOLYFLUOROCARBOXYLIC ACID ESTERS, B-ALKOXYPOLYFLUOROALDEHYDES AND B-ALKOXYPOLYFLUOROKETONES. 